KR100249114B1 - Use of 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivatives as biocidal agents - Google Patents

Abstract

PCT No. PCT/EP92/02248 Sec. 371 Date May 19, 1994 Sec. 102(e) Date May 19, 1994 PCT Filed Sep. 29, 1992 PCT Pub. No. WO93/09670 PCT Pub. Date May 27, 19931,3,5-Triazine-2,4,6-tris-alkylaminocarboxylic acid derivatives of the general formula (I): 1,3,5-triazine-2,4,6-tris[NH-(CH2)n-CO-O-R1] are employed as biocidal or biostatic agents in aqueous systems, in particular in cooling lubricants. Fungicides, for example pyrithione or derivatives thereof and/or N-alkyl-diazenium dioxide salts, can be added to the aqueous systems. 0.05 to 0.40% by weight of the 1,3,5-triazine-2,4,6-alkylaminocarboxylic acid derivatives and 0.0001 to 0.2% by weight of fungicides are sufficient to maintain the biocidal or biostatic actions.

Description

Use of 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivative as bactericide in aqueous system

The present invention relates to 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid, its use as an antiseptic or bacteriostatic agent in an aqueous system and a cooling lubricant containing the same. Triazinecarboxylic acids based on derivatives, ie 2,4,6-tris (omega'-carboxyalkyl, referred to below as 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid) Amino) -1,3,5-triazines are disclosed in J. Prakt. Chemie, 23 (1963), pages 173 to 185 and EP-B 0 046 139. EP-B 0 046 139 relates to the use of the above-mentioned triazinecarboxylic acids and their alkali metals and mono-, di- or triethanolammonium salts as corrosion inhibitors in aqueous systems.

Anticorrosive agents consisting of imidazoline, one of the aforementioned triazinetricarboxylic acids and at least one mono-, di- or trialkanolamine and water are disclosed in EP-A 0 262 086. Corrosion inhibitors according to EP-B 0 046 139 and EP-A 0 262 086 are applied to aqueous systems, for example coolants, cooling lubricants, paints or cleaning agents and the like and further additives, for example Fungicides and the like. Additives conventionally used are halogen containing compounds and reaction products of, for example, boric acid and boric acid with alkanolamines. See literature (Ullmanns Encyklop die der technischen Chemie (Ullmann's Encyclopedia of Indus-trial chemistry), 4th Edition, Volume 8, Verlag Chemie, Weinheim 1974, pages 653-655. In other cases formaldehyde or formaldehyde derivatives have been added as fungicides. However, halogen containing compounds, boric acid and boric acid derivatives and also formaldehyde and derivatives thereof are undesirable for various reasons. Thus, there is an increasing demand for fungicides that can be used in aqueous systems other than halogen-containing compounds, formaldehyde, formaldehyde derivatives, boric acid or boric acid derivatives.

The present inventors have found that the 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivative of the general formula (I) can be used as a bactericide or bacteriostatic agent in an aqueous system.

Wherein n represents a number ranging from 4 to 11, and R ¹ represents

a) alkali metal atom or alkanolamine of the following general formula (II)

(R ² ) ₃ N (II)

Wherein at least one R ² is aa) a hydroxyalkyl group having 2 to 4 carbon atoms, bb) a hydroxyalkyl-oxyalkylene group having 2 to 4 carbon atoms or a cc) to 3 carbon atoms, respectively 6 represents a dihydroxyalkyl group wherein less than 3 R ² groups have the above meaning, the other group of R ² is hydrogen, or if one group of R ² is as mentioned above, the second group is 1 to Ammonium ion from 6 alkyl group, and the third group is hydrogen;

b) one of the alkanolamine radicals of the general formula (II).

According to a preferred embodiment of the invention, 1,3,5-triazine-2,4,6-tris-alkylamino of formula (I) wherein n represents a number in the range of 4 to 8, preferably 5 Carboxylic acid derivatives are used.

Alkali metal atoms may be lithium, sodium or potassium.

Alkanolamines of general formula (II) contain primary, secondary or tertiary amino and free hydroxyl groups. Both amides and esters are in equilibrium with each other and may be formed in the reaction of carboxyl with alkanolamines containing primary or secondary amino groups. See “Surfactants in Consumer Products”, editor J. Falbe, Springer-Verlag, Heidelberg 1987, page 96. Specifically, 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid and alkanols yielding compounds of formula (I) wherein R¹ is an alkanolamine radical according to definition b). Reaction products with amines are referred to herein only as aminoesters. However, those skilled in the art will readily understand that the 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivatives defined above also include the corresponding alkanolamides.

Typical examples of hydroxyalkyl groups having 2 to 4 carbon atoms which may form R 2 groups are 2-hydroxyethyl, 1-methyl-2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxy Butyl, 4-hydroxybutyl and 2-methyl-2-hydroxypropyl groups; Typical examples of hydroxyalkyl-oxyalkylene groups having 2 to 4 carbon atoms in each case in the hydroxyalkyl and oxyalkylene radicals are hydroxyethyl-oxyethylene, hydroxypropyl-oxyethylene, hydroxyethyl-diethyleneoxy, Typical examples of hydroxyethyl-oxypropylene and hydroxypropyl-oxypropylene groups, and dihydroxyalkyl groups having 3 to 6 carbon atoms are 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, 1,3- Dihydroxypropyl and 1,3-dihydroxy-2-methyl or ethyl-propyl groups; And also hydroxyethyl-, hydroxypropyl- and hydroxybutyl-oxybutylene groups.

Compounds of the general formula (I) wherein R¹ represents an alkanolamine radical of the general formula (II) or an ammonium ion derived from the alkanolamine are formulated by the following general formula (III)

1,3,5-triazine-2,4,6-tris [NH- (CH₂) _n -CO-O-R¹] (III)

Wherein n is as defined above, and is obtained by reacting 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid with alkanolamine of general formula (II).

Reaction with a molar excess of alkanolamine relative to 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid is preferred. The unreacted portion of the alkanolamine can be reacted with an organic acid selected from groups formed by straight or branched, saturated or unsaturated fatty acids to bring the pH to 4.5-9.5. Examples of the fatty acids mentioned above include peptanic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid , Octadecanoic acid, nonadecanoic acid, eicosanic acid, heneic acid, docoic acid, 10-undecenoic acid, 9c-dodecenoic acid, 9c-tetradecenoic acid, 9c-hexadecenoic acid, 6c-octadecenoic acid, 6t- Octadecenoic acid, 9c-octadecenoic acid, 9t-octadecenoic acid, 9c, 12c-octadecadienoic acid, 9t, 12t-octadecadienoic acid, 9c, 12c, 15c-octadecatenoic acid, 9c, 11t, 13t-octadecatenic acid, 9c-eicosenoic acid, 5,8,11,14-eicosatetraic acid, 13c-docosenoic acid, 13t-docosenoic acid, 4,8,12,15,19-docosapenta Ethic acid, 12-hydroxy-octanoic acid, and 12-hydroxy-9c-octadecenoic acid, where c represents a double bond and t represents a trans double bond, and industrial grade mixtures thereof and the like. Fatty acids and fatty acid mixtures available from renewable materials, in particular vegetable and / or animal fats and oils, for example capronic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid And even more preferred are ricinoleic acid, linoleic acid, erucin acid and behenic acid.

Preferably, the half of the alkanolamine is reacted with a straight or branched chain, saturated or unsaturated fatty acid having 5 to 11 carbon atoms. If a stable solution or emulsion cannot be obtained by the above method, the desired hydrophilic / hydrophobic balance can be achieved by further using straight or branched chain, saturated or unsaturated fatty acids having 12 to 22 carbon atoms.

Compounds of the general formula (I) which do not use secondary or tertiary amino functional groups are preferably used. Secondary amines and alkanolamines can form stable nitrosoamines with undesirable nitrite ions. Under certain circumstances, tertiary amines and alkanolamines may form secondary amines or alkanolamines by dealkylation. In contrast, primary amines typically do not form stable nitrosoamines but rapidly decompose temporarily formed nitrosoamines and are therefore used as capture agents for nitrite ions. Nevertheless, when using compounds of the general formula (I) derived from secondary alkanolamines, the formation of unstable primary amines occurs more quickly than the formation of secondary nitrosoamines, so that mixtures of primary and secondary alkanolamines Preference is given to using.

On the other hand, the present invention is therefore stable in the absence of secondary or tertiary amino functional groups to form a stable nitroso compound, or when analogous compounds of general formula (I) containing secondary or tertiary amino functional groups are present at the same time It relates to the use of a compound of formula (I) to prevent the formation of nitroso bacteriostatic compounds.

Monocarboxylic acid alkanolamide and 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid alkanolamide and, where appropriate, monocarboxylic acid and / or 1,3, Sterilization and mixtures of alkanolammonium salts of 5-triazine-2,4,6-2 tris-alkylaminocarboxylic acids are also preferably used.

The above mentioned sterilizing and bacteriostatic mixtures can be prepared by mixing the individual components. However, these are conveniently monocarboxylic acids and 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acids of general formula (III), wherein n is the general formula (II) And alkanolamide or alkanolammonium salts from themselves, preferably in excess alkanolamine.

Primary alkanolamines or mixtures of primary and secondary alkanolamines are preferably used.

10 to 50 moles of amine of the general formula (II), in particular 10 to 30 moles and 0.5 to 5 moles of monocarboxylic acid, per mole of 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid It is preferably used.

The reaction is carried out at a temperature in the range from 50 to 180 ° C. Alkanolammonium salts are preferably obtained at temperatures of 50 to 100 ° C., and alkanolamides are obtained at temperatures of> 100 to 180 ° C., in particular 130 to 180 ° C.

The monocarboxylic acids used are linear or branched, saturated or unsaturated fatty acids having 3 to 22 carbon atoms, in particular 12 to 22 carbon atoms, reacted with alkanolamine in the first step and then added to the 1,3,5-tri React with azine-2,4,6-tris-alkylaminocarboxylic acid. The reaction can also be carried out in a different order or in a single step, but a mixture with less pronounced bactericidal or bacteriostatic properties is obtained.

The monocarboxylic acid further used is an ether-carboxylic acid of the following general formula (IV).

R³- (OC _m H _2m ) _q -O-CH ₂ -COOH (Ⅳ)

Wherein R 3 represents a straight or branched chain alkyl or alkenyl group having 9 to 18 carbon atoms, m represents a number of 2 and / or 3, q represents 0 to 100, preferably 0 to 20 Indicates. Wherein the reaction can be carried out in any desired order or in a single step.

Another monocarboxylic acid to be used is an arylsulfonamidocarboxylic acid of the following general formula (Va) and / or an alkylsulfone 1 amidocarboxylic acid of the following general formula (Vb) and / or a general formula (Vc) Half-ester or semi-amide.

(R ') Aryl-SO ₂ -N (R ⁵ ) -R ⁶ -COOH (Va)

R ⁷ -SO ₂ -NR ⁸ -CH ₂ -COOH (Vb)

R ⁹ -OOC-R ¹⁰ -COOH (Vc)

In the formula, R 'represents hydrogen or methyl or ethyl group or several groups, R ⁵ represents hydrogen or methyl, ethyl, betacyanoethyl or hydroxymethyl group, R ⁶ represents alkyl group having 4 to 6 carbon atoms, Aryl represents a phenyl, naphthyl or anthracenyl radical, R ⁷ represents a straight or branched chain alkyl group having 12 to 22 carbon atoms, R ⁸ represents a hydrogen or -CH ₂ -COOH group, and R ⁹ represents a general formula (II) Is an alkanolamine radical, and R ¹⁰ is an o-phenylene, vinylene or 1,2-ethylene radical. Also here, the reaction can be carried out in any desired order or in a single step. Sulfonamidocarboxylic acid of general formula (Va) or (Vb) reacts with alkanolamine of general formula (II) to form sulfonamidocarboxylic acid aminoalkyl ester, or sulfonamidocarboxylic acid alkanolamide It is not yet possible to determine whether to form a mixture or a mixture thereof. For simplicity the reaction product is always named herein as alkanolamide. The aforementioned sulfonamidocarboxylic acids are known, for example, from DE-C 28 40 112 and DE-A 33 04 164.

The excess alkanolamine contained in the resulting reaction mixture to bring the pH to 4.5 to 9.5 ranges from 3 to 22, preferably from 3 to 11 fatty acids, ether-carboxylic acid of general formula (IV), R 3, m and q are as defined above and / or aryl- or alkylsulfonamidocarboxylic acids of the general formula (Va) or (Vb), wherein R ⁴, R ⁵ , R ⁶ , R ⁷ , R ⁸ And R ⁹ are as defined above.

It is preferable to carry out all the reactions so that the reaction mixture is always kept liquid. This is achieved, for example, with excess alkanolamines.

Finally, 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid of general formula (I) contained in a sterile or bacteriostatic mixture, wherein R 1 and n are as defined above. The fungicides mentioned below per 100 parts by weight may also be added to the reaction mixture after the reaction in an amount of 1 part by weight.

Excess alkanolamines present after the reaction described above are fully or partially neutralized as mentioned above to a suitable pH range with the formation of additional content of alkanolamide or alkanolammonium salts.

Examples of straight or branched chain, saturated or unsaturated fatty acids having 3 to 22 carbon atoms are propanoic acid, the aforementioned fatty acids having 5 to 22 carbon atoms and industrial grade mixtures thereof. Half the products of monocarboxylic acids and alkanolamines can also act as anticorrosive agents in the aqueous system.

Preferred examples of alkanolamines of general formula (II) in which R2 is as mentioned above and which can be used according to the invention are mono-, di- and triethanolamine, mono-, di- and tripropanolamine, mono-, di And triisopropanolamine, 2-amino-1-butanol, 2- (2'-aminoethoxy) ethanol, 2-amino-2-methyl-1-propanol and 2-amino-2-ethyl-1,3- Particular preference is given to alkanolamines having a primary amino group or mixtures thereof with propanediol and alkanolamines having a secondary amino group as mentioned above.

In addition to having a single hydroxyalkyl, hydroxyalkyl-oxyalkylene or dihydroxyalkyl group as defined in R2, alkyl groups having 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl, I-propyl, n Preference is given to secondary alkanolamines substituted by -butyl, I-butyl, pentyl, cyclopentyl, hexyl or cyclohexyl and the like.

Said secondary monoalkanol-monoalkylamines are commercially available and typical examples are methyl-hydroxyethyl-amine, n-butyl-hydroxyethylamine and cyclohexyl-hydroxyethyl-amine and corresponding substitutions. Hydroxypropyl derivatives. Some compounds of formula (I) derived from such monoalkanolmonoalkylamines have been demonstrated to be fungicidal further improving bactericidal in addition to other fungicides.

Examples of alkylene groups having 4 to 6 carbon atoms which can form radicals R ⁶ are butylene, pentylene, hexylene, 2-methyl-propylene, 2-methyl-butylene, 3-methyl-butylene, 2,2 -Dimethyl-propylene and 2,2-dimethyl-butylene groups.

The bactericidal and bacteriostatic action of the 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivatives used according to the invention extends to bacteria, yeast and fungi. The limits between bactericidal and bacteriostatic actions are consistently consistent here. Bactericidal (bacterial-killing) or bacteriostatic (growth-inhibiting) action prevails depending on the amount used or duration of action. In addition to the 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivatives, the use of fungicides also results in synergistic effects, i. Examples of fungicides are potassium, aluminum, tin or copper salts of pyrithione and its derivatives, N-alkyl- or N-aryl-, in particular N-cyclohexyl-diagenium dioxide, for example as metal components (Ullmanns Encyklop die der technischen Chemie (Ullmann's Encyclopedia of Industrial Chemistry), 4th edition, volume 17, Verlag Chemie, Weinheim 1979, page 369), phenol, cresol, 1,2-benzisothiazolin-3-one and derivatives thereof and 2 -Methyl- and 2-octyl-4-isothiazolin-3-one are preferred, with halogen free compounds being preferred. Furthermore, fungicides which are water-soluble and stable against alkalis are preferably used.

According to another preferred embodiment of the invention, pyrithione or a derivative thereof, N-alkyl- or N-aryl-, in particular N-cyclohexyl-diagenium dioxide, for example potassium, aluminum, tin or copper as metal component Salts of and are used as fungicides. Pyrithione is an abbreviation of 2-pyridine-thiol 1-oxide and is in tautomeric equilibrium with 1-hydroxy-2-pyridinethione. Possible derivatives of pyrithione are ammonium, sodium, magnesium and zinc salts and disulfides of 2,2'-dithiobis (pyridine 1,1'-dioxide), pyrithione. Under certain circumstances, the anion of pyrithione can precipitate with heavy metals. In contrast, N-alkyl- and N-aryl-diazenium dioxide salts also have complexability in addition to antifungal properties. Therefore, a mixture of pyrithione or a derivative thereof and the above-mentioned N-alkyldiazenium dioxide salt is preferably used. However, only pyrithione or mixtures thereof can also be used and the fungicidal action is maintained in the absence of significant amounts of heavy metal ions. The combination of the 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivatives according to the invention with the above-mentioned fungicides shows a synergistic effect, and even in very small amounts the number according to the invention It is suitable for use in the system.

According to another preferred embodiment of the present invention, the aqueous system is 0.05 to 0.40% by weight and fungicide 0.0001 to 0.2, based on the total amount of 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivative Weight percent, preferably 0.001 to 0.1 weight percent, in particular 0.001 to 0.002 weight percent.

The invention can be used in any desired aqueous or water-containing systems such as metal pore fluids, refrigerants for cooling circulators, detergents, hydraulic fluids, cosmetics and paints and the like. For use in cosmetics, this is preferably adjusted in the range of pH 4.5 to 7.0 by the above-mentioned method. In contrast, the cooling lubricant is preferably adjusted to a pH of 7.5 to 9.5 range.

According to another preferred embodiment of the invention, 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivatives are used as cooling lubricants.

Cooling lubricants are, for example, aqueous liquids used for cooling and lubrication during drilling, grinding, grinding, turning, cutting, grinding, polishing or screw cutting, or during rolling or softening of metals. These are classified into three types according to the mineral oil content;

a) synthetic refrigeration grease without mineral oil,

b) semi-synthetic cooling lubricant containing about 10 to 60% by weight mineral oil and

c) a cooling lubricant containing about 60 to 80% by weight mineral oil.

The cooling lubricant may further contain polyglycol. Instead of mineral oil it is also possible to use natural or synthetic fatty acid esters such as rapeseed oil or ester oil.

Further additives such as corrosion inhibitors, copper fixatives, antiwear agents, emulsifiers, carriers, precipitants, oxygen-trapping agents, complexing agents or antifoams, etc. can be added to all three types of cooling lubricants.

Examples of corrosion inhibitors include organic acids and salts and esters thereof such as benzoic acid, p-tert-butylbenzoic acid, disodium sebacate, triethanolamine laurate, isononanoic acid, triethanol of p-toloenesulfonamidocarproic acid Amine salts, sodium N-lauroyl sarcosinate or nonylphenoxyacetic acid, or polycarboxylic acids; Nitrogen-containing compounds such as fatty acid alkanolamides, imidazolines, oxazolines, triazoles, triethanolamines, fatty amines and N-acylsarcosines, or inorganic nitrites or nitrates; Phosphorus containing materials such as amine phosphates, phosphonic acids, phosphonates, phosphonocarboxylic acids and phosphinocarboxylic acids, or inorganic phosphates such as NaH ₂ PO ₄ , and sulfur containing materials such as petroleum Salts of sulfonates or alkylbenzenesulfonates or heterocyclic compounds containing one or more sulfur atoms in the ring.

Copper immobilizers that can be used are for example benzotriazole, methylene-bis-benzotriazole, for example sodium 2-mercaptobenzotriazole, thiadiazole, for example 2,5-dimercapto- 1,3,4-thiadiazole derivatives, tolyltriazole, and the like.

Wear resistant agents that can be used are AW (wear resistant) or EP (extreme) additives, for example sulfur, phosphorus or halogen containing materials such as sulfonated fats and olefins, tritolyl phosphate, mono- and phosphorous acid diesters, Preferred are adducts of ethylene oxide and / or propylene oxide, chloroparaffin or ethoxylated phosphate esters, to polyhydroxy compounds optionally partially esterified with fatty acids and chlorine free compounds.

Examples of emulsifiers are ether-carboxylic acids, fatty acid alkanolamides, sodium petroleum sulfonates, mono- or diesters or ethers of polyglycols, polypropylene glycols or mixed polyethylene / polypropylene glycols or fatty acid soaps and the like.

Carriers that can be used are, for example, poly (meth) acrylic acid and salts thereof, hydrolyzed polyacrylonitrile, polyacrylamide and copolymers thereof, ligninsulfonic acid and salts thereof, starch and starch derivatives, cellulose, alkylphosphonic acid, 1-amino-alkyl-1,1-diphosphonic acid and salts thereof, polymaleic acid and other polycarboxylic acids, ester oils, natural or synthetic fatty acid esters such as rapeseed oil or alkali metal phosphates and the like.

Examples of precipitants are alkali metal phosphates or alkali metal carbonates.

Examples of oxygen-trapping agents are alkali metal sulfates, morpholines and hydrazines.

The 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivative according to the present invention has its own complexability. However, other complexing agents may be added, such as phosphonic acid derivatives, nitrilotriacetic acid or ethylenediamine-tetraacetic acid and salts thereof and the like. Moreover, any N-alkyl- and N-aryldiazenium dioxide salts used as fungicides are also complexable as referenced above.

Examples of antifoaming agents are distearyl sebacic acid diamide, distearyladipic acid diamide or ethylene oxide adducts and / or propylene oxide adducts of these amides, fatty alcohols and ethylene oxide adducts thereof and / or propylene oxide Addition products, natural and synthetic waxes, silicone compounds, silicic acid derivatives, and fuming silicon oxide.

The invention thus further provides a) a 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivative, wherein R 1 and n are as defined above, b) fungicides, c) water, d A) mineral oil, where appropriate, e) where appropriate, emulsifiers and / or other auxiliaries; f) where appropriate, corrosion inhibitors, but with respect to the total amount of cooling lubricant 1,3,5-triazine-2,4,6- It relates to a cooling lubricant containing 0.05 to 0.40% by weight of tris-alkylaminocarboxylic acid derivatives and 0.0001 to 0.2% by weight of fungicide, preferably 0.001 to 0.1% by weight, in particular 0.001 to 0.02% by weight.

Particularly preferred cooling lubricants are, as emulsifiers and / or other auxiliaries, a) R 3, m and q in the form of alkanolamides and / or alkanolammonium salts in which R 2 has added alkanolamines of the general formula (II) as defined above. Is an ethercarboxylic acid of general formula (IV) as defined above, b) a straight or branched chain having 12 to 22 carbon atoms, saturated or unsaturated fatty acids and fatty acid alkanolamides based on amines of general formula (II), c) R² R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ in the form of alkanolamide and / or almanolammonium salts to which alkanolamines of formula (II) have been defined as defined above Aryl- and alkylsulfonamidocarboxylic acids of (Va) or (Vb), d) straight or branched, saturated or unsaturated carboxylic acids having 5 to 22, preferably 5 to 11, carbon atoms to pH 7.5 to 9.5 Acids, or e) straight or branched fat of 12 to 18 carbon atoms A compound containing an alcohol.

Other particularly preferred cooling lubricants are those containing pyrithione or derivatives thereof and / or N-alkyldiagenium dioxide salts as fungicides.

Cooling lubricants of the invention can be prepared by mixing the individual components together. If the cooling lubricant of the present invention is intended to contain fatty acid alkanolamides, it is preferable to prepare the compounds of the general formula (I) in the form of a mixture with fatty acid alkanolamides by the above-mentioned method. This method additionally provides the advantage that only a liquid reaction mixture can be obtained and not subjected to further means, for example grinding or dissolving in a suitable solvent.

The invention is explained in more detail below by way of examples of particularly preferred embodiments.

Examples 1 to 25 are simply named triazinecarboxylic acids below which can be obtained commercially or obtained by reacting cyanuric acid chloride with 6-aminohexanoic acid according to EP-B 0 046 139. It relates to a process for the preparation of derivatives used according to the invention of 2,4,6-tris (omega'-carboxypentylamino) -1,3,5-triazine.

Triazinecarboxylic acid can be used as a commercial product or in the form of a commercial aqueous product. Solid product containing about 50% by weight of water was used in the examples below.

75 g (0.714 moles of diethanolamine; 26.7 moles per mole of triazinecarboxylic acid) were heated to 60 ° C. and 25 g (0.0267 moles) of triazinecarboxylic acid were added while stirring until a clear solution was formed. 100 g of a transparent low viscosity liquid were obtained.

Example 2

25 g (0.0267 mol) of triazinecarboxylic acid was added while stirring 75 g (0.714 mol) of diethanolamine. After reacting for several hours at 150 to 160 ° C, 10 g of water was distilled off. The final acid value was 10 mg KOH / g. 90 g of a clear medium-viscosity liquid was obtained.

Example 3

75 g (1.230 mole of monoethanolamine; 46.1 mole per mole of triazinecarboxylic acid) were heated to 60 ° C. and 25 g (00267 moles) of triazinecarboxylic acid were added and stirred until a clear solution was formed. 100 g of a transparent low viscosity liquid were obtained.

Example 4

75 g (1.230 mole) of monoethanolamine was added 25 g (0.0267 mole) of triazinecarboxylic acid at 60 ° C. with stirring, and the mixture was heated to 140 to 143 ° C. After reacting for 10 hours, 18 g of water was distilled off. The final acid value was 12 mg KOH / g. A white solid product was obtained.

Example 5

75 g (0.843 moles; 31.5 moles per mole of triazinecarboxylic acid) of 2-amino-1-butanol were heated to 60 ° C. and 25 g (0.0267 moles) of triazinecarboxylic acid were added until the solution formed. 100 g of a transparent low viscosity liquid were obtained.

Example 6

863 g (9.697 moles; 31.5 moles per mole of triazinecarboxylic acid) of 2-amino-1-butanol were added at 60 ° C. with stirring, 287 g (0.307 moles) of triazinecarboxylic acid and the mixture was heated to 145 ° C. After reacting for 20 hours, 150 g of water was distilled off. The final acid value was 10 mg KOH / g. 1000 g of transparent low viscosity liquid was obtained.

Example 7

While stirring 75 g (0.714 mol; 2-6.7 mol per mol of triazinecarboxylic acid) of 2- (2'-aminoethoxy) ethanol, 25 g (0.0267 mol) of triazinecarboxylic acid were added at 60 DEG C until a clear solution was formed. It was. 100 g of a transparent low viscosity liquid were obtained.

Example 8

125 g (0.134 mole) of triazinecarboxylic acid were added at 60 ° C. while stirring 375 g (3.571 mole; 26.7 mole per mole of triazinecarboxylic acid) of 2- (2′-aminoethoxy) ethanol and the mixture was heated to 145 ° C. It was. After reacting for 16 hours, 73 g of water was distilled off. The final acid value was 7 mg KOH / g. 427 g of a white paste product were obtained.

Example 9

20 g (0.190 mol; 7.1 mol per mol of triazinecarboxylic acid) and 55 g (0.618 mol; 23.1 mol per mol of triazinecarboxylic acid) of 2- (2'-aminoethoxy) ethanol Heated to 60 ° C. and 25 g (0.0267 mol) of triazinecarboxylic acid was added and stirred until a clear solution formed. 100 g of a transparent low viscosity liquid were obtained.

Example 10

228 g (2.171 mole; 7.1 mole per mole of triazinecarboxylic acid) and 627 g (7.045 mole; 23.1 mole per mole of triazinecarboxylic acid) of 2-amino-1-butanol 285 g (0.304 mol) of triazinecarboxylic acid were added and stirred at 60 ° C, and the mixture was heated to 145 ° C. After reacting for 16 hours, 140 g of water was distilled off. The final acid value was 13 mg KOH / g. 1000 g of a clear medium-viscosity liquid was obtained.

Example 11

75 g (0.758 mol; 28.4 mol per mol of triazinecarboxylic acid) of AMP 90 (2-amino-2-methyl-1-propanol with 10% water) was heated to 60 DEG C and 25 g (0.0267 mol of triazinecarboxylic acid) ) Was stirred until a clear solution was formed. A clear low viscosity liquid was obtained.

Example 12

833 g (8.424 moles; 31.5 moles per mole of triazinecarboxylic acid) of AMP 90 were heated to 60 ° C, 250 g (0.267 moles) of triazinecarboxylic acid were added and stirred, and the mixture was heated to 140 to 145 ° C. After reacting for 20 hours, 240 g of water was distilled off. The final acid value was 15 mg KOH / g. 843 g of a nearly clear high viscosity product was obtained.

Example 13

75 g (0.630 mol; 23.6 mol per mol of triazinecarboxylic acid) of AEPD (2-amino-2-ethyl-1,3-propanediol) were heated to 60 ° C and 25 g (0.0267 mol) of triazinecarboxylic acid were added. Stir until a clear solution is formed. 100 g of a clear medium-viscosity liquid were obtained.

Example 14

990 g of AEPD (8.319 moles; 23.6 moles per mole of triazinecarboxylic acid) were heated to 60 ° C., 330 g (0.5 mole) of triazinecarboxylic acid was added and stirred and the mixture was heated to 140-145 ° C. After reacting for 16 hours, 320 g of water was distilled off. The final acid value was 10 mg KOH / g. 1000 g of a clear, high viscosity liquid was obtained.

Example 15

75 g of monoisopropanolamine (1.000 moles; 37.4 moles per mole of triazinecarboxylic acid) were heated to 60 ° C. and 25 g (0.0267 moles) of triazinecarboxylic acid were added and stirred until a clear solution was obtained. 100 g of low viscosity liquids were obtained.

Example 16

375 g of monoisopropanolamine (5.000 moles; 37.4 moles per mole of triazinecarboxylic acid) were heated to 60 ° C., 125 g (0.134 moles) of triazinecarboxylic acid were added and stirred, and the mixture was heated to 140 ° C. After reacting for 16 hours, 74 g of water was distilled off. The final acid value was 12 mg KOH / g. 426 g of a transparent low viscosity liquid were obtained.

Example 17

75 g (0.503 mol; 18.9 mol per mol of triazinecarboxylic acid) were heated to 60 DEG C and 25 g (0.0267 mol) of triazinecarboxylic acid were added and stirred until a clear solution was obtained. 100 g of a transparent low viscosity liquid were obtained.

Example 18

750 g of triethanolamine (5.034 moles; 18.9 moles per mole of triazinecarboxylic acid) were heated to 60 ° C, 250 g (0.267 moles) of triazinecarboxylic acid were added and stirred, and the mixture was heated to 140 to 150 ° C. After reacting for 16 hours, 130 g of water was distilled off. The final acid value was 6 mg KOH / g. 870 g of a clear medium viscosity liquid were obtained.

Example 19

8 parts by weight of triazinecarboxylic acid and 1 part by weight of 2- (80heptadecenyl) -4,5-dihydro-1- (2-hydroxyethyl) -imidazole 6 parts by weight of monoisopropanolamine while stirring at room temperature Wealth was added. The mixture was stirred until a clear brown liquid formed.

Example 20

[Step 1]

130 g (1.238 moles of 2- (2'-aminoethoxy) ethanol; 4.8 moles per mole of triazinecarboxylic acid) and 370 g (4.157 moles; 16.2 moles of mole of triazinecarboxylic acid) of 2-amino-1-butanol It was reacted with 190 g (0.674 mol; 2.6 mol per mol of triazinecarboxylic acid) at 145 ° C. After reacting for 10 hours, 12 g of water was distilled off. 678 g of a liquid product having an acid value of 7 mg KOH / g were obtained.

[Step 2]

678 g of the product of the first step was heated to 70 DEG C and 240 g (0.0256 mol) of triazinecarboxylic acid was added and stirred. A clear viscous solution was obtained.

Example 20a

[Step 1]

130 g (1.238 mol) of 2- (2'-aminoethoxy) ethanol and 370 g (4.157 mol) of 2-amino-1-butanol were reacted with 190 g (0.674 mol) of olefins at 145 ° C. After reacting for 10 hours, 12 g of water was distilled off. 678 g of a liquid product having an acid value of 7 mg KOH / g were obtained.

[Step 2]

A commercially available arylsulfonamidocarboxylic acid (Hostacor ^R H liquid) having 678 g of the product of the first stage heated to 70 ° C., 240 g (0.256 mol) of triazinecarboxylic acid and a molecular weight of about 350 (hereinafter referred to as sulfonamido) 174 g (0.497 mol; 1.9 mol per mol of triazinecarboxylic acid) were added and stirred. A stable, slightly cloudy liquid was obtained.

Example 20b

[Step 1]

130 g (1.238 mol) of 2- (2'-aminoethoxy) ethanol and 370 g (4.157 mol) of 2-amino-1-butanol were reacted with 190 g (0.674 mol) of olefins at 145 ° C. After reacting for 10 hours, 12 g of water was distilled off. 678 g of a liquid product having an acid value of 7 mg KOH / g were obtained.

[Step 2]

678 g of the product of the first stage was heated to 70 ° C. and chloroacetic acid was obtained by condensation of 240 g (0.0256 mole) of triazinecarboxylic acid and molecular weight of ether-carboxylic acid (1 mole of industrial grade oleyl alcohol with 10 moles of ethylene oxide). 106 g (0.148 mol; 0.6 mol per mol of triazinecarboxylic acid) were added and stirred. A clear viscous liquid was obtained.

Example 20c

130 g (1.238 mole) of 2- (2'-aminoethoxy) ethanol and 370 g (4.157 mole) of 2-amino-1-butanol were heated to 70 ° C. and 174 g (0.497 mole) of sulfonamidocarboxylic acid and tri 240 g (0.256 mol) of azinecarboxylic acid was added and stirred. A pale, transparent, medium viscosity liquid was obtained.

Example 20d

130 g (1.238 mol) of 2- (2'-aminoethoxy) ethanol, 370 g (4.157 mol) of 2-amino-1-butanol, 174 g (0.497 mol) of sulfonamidocarboxylic acid and 240 g (0.256 of triazinecarboxylic acid) Mole) was reacted at 145 ° C. After reacting for 12 hours, 143 g of water were distilled off. 771 g of a medium-viscosity clear liquid product having an acid value of 25 mg KOR / g were obtained.

Example 20e

130 g (1.238 mole) of 2- (2'-aminoethoxy) ethanol and 370 g (4.157 mole) of 2-amino-1-butanol were heated to 70 ° C. and 106 g (0.148 mole) of ether-carboxylic acid and triazinecarboxyl 240 g (0.256 mol) of acid was added and stirred. The reaction was carried out at 145 ° C. A pale, medium-viscosity product was obtained.

Example 20f

130 g (1.238 mol) of 2- (2'-aminoethoxy) ethanol, 370 g (4.157 mol) of 2-amino-1-butanol, 106 g (0.148 mol) of ethercarboxylic acid and 240 g (0.256 mol) of triazinecarboxylic acid Was reacted at 145 ° C. After reacting for 13 hours, 137 g of water were distilled off. 709 g of a clear medium-viscosity product were obtained with a final acid value of 20 mg KOH / g.

Example 21

678 g of the product of the first step of Example 20 was heated to 60 ° C., 240 g (0.256 mol) of triazinecarboxylic acid was added and stirred, and the mixture was reacted to 140 to 150 ° C. After reacting for 10 hours, 138 g of water was distilled off. The final acid value was 14 mg KOH / g. 780 g of clear, medium-viscosity product were obtained.

Example 22 (Not in accordance with the present invention)

273 g (1.019 moles; 2.8 moles per mole of triazinecarboxylic acid) of commercially available industrial grade oleyl alcohol (about 90% concentration, about 95% iodine) were heated to 80 to 100 ° C. and 333 g of triazinecarboxylic acid (0.356 mole) was added and stirred slowly and the mixture was heated up to 200 ° C. After reacting for about 20 hours, 206 g of water was distilled off. The final acid value was 18 mg KOH / g. A clear medium-viscosity liquid was obtained.

Example 23 (Not in accordance with the present invention)

350 g (2.692 moles; 15 moles per mole of triazinecarboxylic acid) of 2-ethylhexanol were heated to 100 ° C., 168 g (0.179 moles) of triazinecarboxylic acid was added and stirred and the mixture was heated up to 190 ° C. After reacting for 10 hours, water and 358 g of ethylhexanol were distilled off. The final acid value was 15 mg KOH / g. 160 g of clear viscous liquid was obtained.

Example 24 (Not in accordance with the present invention)

273 g of 1,2-propylene glycol (3.592 moles; 10.1 moles per mole of triazinecarboxylic acid) were heated to 100 ° C., 333 g (0.356 moles) of triazinecarboxylic acid was added and stirred and the mixture was heated up to 168 ° C. After reacting for 7 hours, 276 ml of water was distilled off. The final acid value was 38 mg KOH / g. 330 g of a viscous pale liquid was obtained.

Example 25 (Not in accordance with the present invention)

333 g (0.356 mole) of triazinecarboxylic acid were added to 324 g (3.000 mole of benzyl alcohol; 8.4 moles per mole of triazinecarboxylic acid), and the mixture was heated to a maximum of 180 ° C. under a nitrogen atmosphere. After reacting for 9 hours, 180 ml of water was distilled off. The final acid value was 21 mg KOH / g. 477 g of low viscosity liquid were obtained.

Example 26

125 g (0.13 mol) of triazinecarboxylic acid was added to 375 g (3.2 mol; 23.97 mol per mol of triazinecarboxylic acids) of N-butylethanolamine, and it was made to react at 145 degreeC. After reacting for 14 hours, 85 g of water was distilled off. 415 g of a liquid product having an acid value of 13 mg KOH / g were obtained.

Example 27

167 g (0.18 mol) of triazinecarboxylic acid was added to 167 g (1.43 mol; 8 mol per mol of triazinecarboxylic acids) of N-butylethanolamine, and it was made to react at 148 degreeC. After reacting for 14 hours, 56 g of water was distilled off. 278 g of a viscous product having an acid value of 7 mg KOH / g were obtained.

Example 28

100 g (0.85 mol; 2 mol per mol of triazinecarboxylic acid), 100 g (0.95 mol; 2.22 mol per mol of triazinecarboxylic acid) and monoisopropanol 200 g (0.21 mol) of triazine carboxylic acid was added to 100 g (1.33 mol; 3.11 mol per mol of triazine carboxylic acid) and reacted at 150 ° C. After reacting for 10 hours, 65 g of water was distilled off. 435 g of a medium viscosity product having an acid value of 14 mg KOH / g was obtained.

Example 29

Triazinecarboxyl in 516 g (4.9 moles; 8.75 moles per mole of triazinecarboxylic acid) and 248 g (3.3 moles per mole of triazinecarboxylic acid) of 516 g of 2- (2'-aminoethoxy) ethanol and monoisopropanolamine 526 g (0.56 mol) of acid was added and the mixture was reacted at 150 占 폚. After reacting for 14 hours, 290 g of water were distilled off. An acid value of 1000 g of a liquid product of 11 mg KOH / g was obtained.

Example 30

[Step 1]

117 g (1 mol) of N-butylethanolamine was heated to 110 ° C, and 148 g (1 mol) of phthalic anhydride was slowly added while cooling. The reaction was carried out at 130 ° C. for 4 hours. 265 g of a solid glassy product having an acid value of 211 mg KOH / g was obtained.

[Step 2]

50 g of the product of the first step were mixed with 50 g of the product of Example 10 at 100 ° C. 115 g of viscous product having an acid value of 115 mg KOH / g was obtained.

Example 31

50 g of Korantin PA (2-methyl-2-ethylhexylamide) were mixed with 50 g of the product of Example 10 at 50 ° C. A viscous product with an acid value of 88 mg KOH / g was obtained.

[Comparative Examples 1 to 3 and Examples 32 to 54]

Many 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivatives prepared are formulated with water, spindle oil and, in each case, other additives specified in some examples, such as fungicides, to form water. A mixture was obtained which resulted in a cooling lubricant diluted from: 20 to 1:80.

Further mixtures without bactericides were formulated in Comparative Examples 1 and 2 and mixtures with boric acid alkanolamine condensation products as bactericides were formulated in Comparative Example 3. The following percentages are in parts by weight. The information in the "Yes" column is described in Table 1. All chemicals listed in Table 1 are commercially available.

Table 1: Description

1.Deoil distillate of 25-30% resin (acid value 155-190)

2.a) isononanoic acid

b) 2,2-dimethyl-octanoic acid

3. Spindle oil, viscosity 22 ℃ / s at 40 ℃

4. a) Reaction product (ether-carboxylic acid) in which a condensation product of 1 mol of industrial grade oleyl alcohol and 10 mol of ethylene oxide is reacted with 1 mol of chloroacetic acid

b) a reaction product of a condensation product of 1 mole of C ₉ -C ₁₃ -oxo-alcohol with 3 moles of ethylene oxide and 2 moles of propylene oxide with 1 mole of chloroacetic acid (ether-carboxylic acid)

5.a) Industrial grade oleyl alcohol (approx. 90% concentration, iodine approx. 95)

b) 2-hexyl-decanol

6. a) Condensation product of 1 mole of industrial grade mixture of oleyl and cetyl alcohol with 5 moles of ethylene oxide

b) fatty alcohol polyglycol ether (Emulsogen ^R LP)

7. a) 40 parts by weight of diethanolamine and 60 parts by weight of olein condensation product.

b) A mixture of 20% ethanol amine added to a) relative to the total amount of condensation product and ethanolamine.

8. a) Diethylene Glycol

b) butyldiglycol

c) butyl glycol

9. a) Sodium Petroleum Sulfonate with a Molecular Weight of about 460

b) sodium alkylbenzenesulfonate having a molecular weight of about 350

10. 50% potassium hydroxide solution

11.10% N- (cyclohexyl-diagenium dioxide) potassium hydrate 10% propylene glycol 70% demineralized water in hydrated form in 30% aqueous solution of sodium salt of 10% pyrithione

12. Condensation product of 1 mole of boric acid and 3 moles of ethanolamine

13. Arylsulfonamidocarboxylic acid of about 350 molecular weight (Hostacor ^R H liquid; acid value about 90%, residue solubilizer)

Comparative Example 1 Example

7% Fatty Acid 1

2% sulphate 9b)

5% fatty acid alkanolamide 7b)

2% supplement 8a)

1% Supplement 10

83% spindle oil 3

Comparative Example 2 Example

8% Fatty Acid 1

17% sulphate 9a)

4% fatty acid alkanolamide 7a)

3% supplements 8c)

2% supplements 10

36% Spindle oil 3

30% water

Comparative Example 3 Example

20% Boric Acid Product 12

10% fatty acids 1

10% fatty acid alkanolami 7a)

10% supplements 8b)

20% Spindle Oil 3

30% water

Example 32 Example

25% Example 1

31% Spindle oil 3

10% fatty acids 1

5% fatty acid 2b)

4% ether-carboxylic acid 4b)

6% fatty acid 5a)

5% nonionic emulsifier 6a)

1% Fungicide 11

13% water

Example 33 Example

25% Example 2

31% Spindle oil 3

10% fatty acids 1

5% fatty acid 2b)

4% ether-carboxylic acid 4b)

6% fatty alcohol 5a)

14% water

5% nonionic emulsifier 6a)

Example 34 Example

25% Example 4

31% Spindle oil 3

10% fatty acids 1

5% fatty acid 2b)

4% ether-carboxylic acid 4b)

6% fatty alcohol 5a)

5% nonionic surfactant 6a)

14% water

Example 35 Example

22% Example 6

11% fatty acid 2a)

17% Fatty Acid 1

6% ether-carboxylic acid 4a)

9% fatty acid alkanolamide 7a)

4% fatty alcohol 5a)

22% Spindle Oil 3

8% water

1% Fungicide 11

Example 36 Example

21% Example 10

21% Fatty Acid 1

11% fatty acid 2a)

7% ether-carboxylic acid 4a)

5% fatty alcohol 5b)

20% Spindle Oil 3

13% water

2% Fungicides 11

Example 37 Example

25% Example 14

31% Spindle oil 3

10% fatty acids 1

3% fatty acid 2a)

8% fatty alcohol 5a)

5% nonionic emulsifier 6a)

4% ether-carboxylic acid 4a)

1% Fungicide 11

13% water

Example 38 Example

25% Example 16

31% Spindle oil 3

10% fatty acids 1

5% fatty acid 2b)

4% ether-carboxylic acid 4b)

6% fatty alcohol 5a)

5% nonionic emulsifier 6a)

1% Fungicide 11

13% water

Example 39 Example

35% Example 17

20% Spindle Oil 3

10% fatty acids 1

5% fatty acid 2a)

3% ether-carboxylic acid 4b)

6% fatty alcohol 5b)

5% nonionic surfactant 6a)

16% water

Example 40 Example

19% Example 21

29% Fatty Acid 1

29% spindle oil 3

5% supplements 8b)

3% nonionic emulsifier 6b)

1% Fungicide 11

14% water

Example 41 Example

22% Example 3

20% Fatty Acid 1

16% fatty acid 2a)

7% ether-carboxylic acid 4a)

5% fatty alcohol 5b)

18% Spindle Oil 3

2% Fungicides 11

12% water

Example 42 Example

21% Example 9

21% Fatty Acid 1

11% fatty acid 2a)

7% ether-carboxylic acid 4a)

5% fatty alcohol 5b)

20% Spindle Oil 3

2% Fungicides 11

13% water

Example 43 (Not in accordance with the invention)

7% Example 25

93% Comparative Example 1

Example 44 (Not in accordance with the invention)

7% Example 25

91% Comparative Example 1

2% Fungicides 11

Example 45 (not in accordance with the invention)

4% Example 23

96% Comparative Example 1

Example 46 (Not in accordance with the invention)

4% Example 23

94% Comparative Example 1

2% Fungicides 11

Example 47 (does not comply with the invention)

4% Example 23

96% Comparative Example 2

[Example 48 (Not According to the Invention)] Yes

4% Example 23

94% Comparative Example 2

2% Fungicides 11

Example 49

24% Example 20a

22% Fatty Acid 1

29% spindle oil 3

4% supplements 8b)

2% monoethanolamine

4% nonionic emulsifier 6a)

1% Fungicide 11

14% water

Example 50

25% Example 20b

23% Fatty Acid 1

29% spindle oil 3

3% supplements 8b)

4% nonionic emulsifier 6a)

1% Fungicide 11

14% water

1% monoethanolamine

Example 51 Example

23% Example 20c

28% Fatty Acid 1

1% fatty alcohol 5a)

4% nonionic surfactant 6a)

4% 8b

1% fungicide 11

27% spindle oil 3

12% water

Example 52 Example

23% Example 20d

28% Fatty Acid 1

25% spindle oil 3

5% nonionic emulsifier 6b)

2% fatty alcohol 5b)

2% supplements 8b)

1% Fungicide 11

14% water

Example 53 Example

23% Example 20e

28% Fatty Acid 1

1% fatty alcohol 5a)

4% nonionic emulsifier 6a)

4% supplements 8b)

1% Fungicide 11

27% spindle oil 3

12% water

Example 54 Example

23% Example 20f

28% Fatty Acid 1

1% fatty alcohol 5a)

4% nonionic emulsifier 6a)

4% supplements 8b)

1% Fungicide 11

27% spindle oil 3

12% water

Example 55 Example

21% Example 32

21% Fatty Acid 1

20% Spindle Oil 3

15.5% water

1.5% ether-carboxylic acid 4b)

2% ether-carboxylic acid 4a)

2% nonionic emulsifier 6b)

5% fatty alcohol 5b)

11% fatty acid 2a)

1% monoethanolamine

Example 55a

98% Example 55

2% Fungicides 11

Example 56 Example

10% Example 33

30% spindle oil 3

22% water

15% fatty acids 1

5% fatty acid 2a)

5% fatty alcohol 5b)

2% ether-carboxylic acid 4b)

4% ether-carboxylic acid 4a)

3% monoethanolamine

4% fatty acid alkanolamide 7a)

Example 56a

98% Example 56

2% Fungicides 11

Example 57 Example

10% Example 34

23% fatty acid 2a)

9% monoethanolamine

2% ether-carboxylic acid 4b)

6% fatty alkanolamide 7a)

50% water

Example 57a

98% Example 57

2% Fungicides 11

Example 58 Example

5% Example 33

5% Example 35

23% fatty acid 2a)

10% monoethanolamine

2.5% ether-carboxylic acid 4b)

6% fatty acid alkanolamide 7a)

48.5% water

Example 58a

98% Example 58

2% fatty acids 11

Example 59 Example

20% Example 37

25% spindle oil 3

17% Fatty Acid 1

4% fatty alcohol 5b)

4% nonionic emulsifier 6b)

1% monoethanolamine

29% water

Example 59a

98% Example 60

2% Fungicides 11

Example 60 Example

20% Example 37

25% spindle oil 3

17% Fatty Acid 1

4% fatty alcohol 5b)

4% nonionic emulsifier 6b)

1% monoethanolamine

29% water

Example 60a Example

98% Example 60

2% Fungicides 11

[Microbiological test method]

In-house developed inoculation cycle tests were performed. For this purpose the following dilutions of Comparative Examples 1 to 3 and Examples 26 to 42 were prepared with Hamburg tap water: 1.25%, 2.5% and 5.0% (corresponding to 1:80, 1:40 and 1:20)

Samples were inoculated several times with concentrated mixed pathogens. Pathogens contained bacterial yeasts and fungi from effluent emulsion systems of various origins. The total cell count was about 10 ⁷ bacteria / ml.

The amount of mixed pathogen for sample inoculation corresponds to six times the amount proposed according to DAB 9 (German Pharmacopoeia). 6 ml of pathogen solution was used per 100 ml of sample. The method (KH Wallh Praxis der Sterilisation-Desinfektion-Konservierung-Keimidentifizierung (Practice of Steriliz-ation-Disinfection-Preservation-GermIdentification), 4th Edition, Georg Thieme Verlag, Stuttgart 1988) (up to 6 times) Samples were inoculated until no detection was made. In my experience, the first dose was DAB 9 / caller Corresponds to the 3 vaccination cycle by βer) method.

The method has the following advantages.

1. Use mixed pathogens that actually occur.

2. The sample is exposed several times to large inoculation bacteria.

3. This method is fast and suitable for industrial use. Compared to conventional methods, which take months, results can be obtained within up to eight weeks if there is no need to repeat.

4. Determination of the useful life of the emulsion used in the central system can be derived from the results.

The action time of the microorganisms on the sample was about 1 week. After this period the samples were inverted and incubated on two specific nutrient media in each case. The number of colonies was measured under a microscope and the number of bacteria per ml of sample was determined therefrom. Table 2 shows the number of inoculation cycles in which the first infiltration of bacteria was observed. This is a measure of fungicide activity in a particular sample. The formulations of Examples 33,34,35 based on the compounds of Examples 2,4,6 and 16 have proven particularly active. Example 34 further showed fungicidal action without addition of pyrithione or a derivative thereof. When comparing Examples 32 and 42 with Examples 33 and 36, respectively, we further found that alkanolamides were significantly more active than alkanolammonium salts derived from the same alkanolamines.

TABLE 2

TABLE 2a

Claims (10)

a) 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivatives of general formula (I): b) fungicides, where appropriate, c) water, d) mineral oil, where appropriate e) where appropriate, emulsifiers and / or other auxiliaries, f) where appropriate, corrosion inhibitors, and with respect to the total amount of cooling lubricant, 1,3,5-triazine-2,4,6-tris-alkylamino A cooling lubricant containing 0.05 to 0.40% by weight of carboxylic acid derivative and 0.0001 to 0.2% by weight of fungicide. 1,3,5-triazine-2,4,6-tris [NH- (CH ₂ ) _n -CO-O-R¹] (I) In the formula, n represents an integer ranging from 4 to 11, R¹ is alkanolamine of the general formula (II) (R²) ₃ N (Ⅱ) Wherein at least one R2 is aa) a hydroxyalkyl group having 2 to 4 carbon atoms, bb) a hydroxyalkyl-oxyalkylene or cc) having 3 to 6 carbon atoms, each having 2 to 4 carbon atoms Dihydroxyalkyl group wherein less than three R 2 groups have the above meaning, the other group of R 2 is hydrogen, or if one group of R 2 is as mentioned above, the second group is an alkyl group having 1 to 6 carbon atoms, Tertiary group is hydrogen] ammonium ions from hydrogen or alkanolamine radicals of general formula (III). The process of claim 1, wherein the cooling lubricant is emulsifier and / or other adjuvant, wherein a) R2 is in the form of an alkanolamide and / or alkanolammonium salt with an alkanolamine of general formula (II) as defined above. Ether-carboxylic acid of the following general formula (IV) R³- (OC _m H _2m ) -O-CH ₂ -COOH (Ⅳ) Wherein R 3 represents a straight or branched chain alkyl or alkenyl group having 9 to 18 carbon atoms, m represents a number of 2 and / or 3, q represents a number of 0 to 20, b) Arylsulfonamidocarboxylic acids of the general formula (Va) in the form of alkanolamides and / or alkynol ammonium salts with alkanolamines of general formula (II) as defined above (R ') Aryl-SO ₂ -N (R ⁵ ) -R ⁶ -COOH (Va) [Wherein R 'represents hydrogen or methyl or an ether group or several groups, R ⁵ represents hydrogen or methyl, ethyl, beta-cyanoethyl or hydroxymethyl group, and R ⁶ represents an alkylene group having 4 to 6 carbon atoms And aryl represents a phenyl, naphthyl or atracenyl radical] or an alkylsulfonamidocarboxylic acid of the general formula (Vb) R ⁷ -SO ₂ -NR ⁸ -CH ₂ -COOH (Vb) Wherein R ⁷ represents a straight or branched chain alkyl group having 12 to 22 carbon atoms or a semi-ester or semi-amide of the following general formula (Vc) R ⁹ -OOC-R ¹⁰ -COOH (Vc) [Wherein R ⁹ is an alkanolamine radical of general formula (II) and R ¹⁰ is a ₀ -phenylene, vinylene or 1,2-ethylene radical], c) for the range of pH 7.5 to 9.5 Straight or branched chain of 5 to 22 carbon atoms, saturated or unsaturated carboxylic acids, d) straight or branched chain carbon atoms of 12 to 18, saturated or unsaturated fatty alcohols and / or e) straight or branched chain of 12 to 22 carbon atoms, A cooling lubricant, characterized in that saturated or unsaturated fatty acids and R2 contain fatty acid alkanolamides based on amines of the general formula (II) as defined above. The cooling lubricant according to claim 1 or 2, which contains pyrithione or a derivative thereof and / or an N-alkyl-diagenium dioxide salt as a fungicide. A bactericide or bacteriostatic agent in an aqueous system, containing 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivative of the following general formula (I). 1,3,5-triazine-2,4,6-tris [NH- (CH₂) _n -CO-O-R¹] (Ⅰ) Wherein n represents a number ranging from 4 to 11, and R¹ is a) an alkali metal atom or an alkanolamine of the general formula (II) (R²) ₃ N (Ⅱ) Wherein at least one R2 is aa) a hydroxyalkyl group having 2 to 4 carbon atoms, bb) a hydroxyalkyl-oxyalkylene group having 2 to 4 carbon atoms each, or cc) 3 to 6 carbon atoms When less than 3 R 2 groups have the above meaning, the other group of R 2 is hydrogen, or if one group of R 2 is as mentioned above, the second group is an alkyl group having 1 to 6 carbon atoms , A third group is hydrogen; b) one of the alkanolamine radicals of formula (II). The fungicide or bacteriostatic agent according to claim 4, wherein n represents a number of five. 6. A amine according to claim 4 or 5, wherein the amine of formula (II) is a primary alkanolamine or a mixture of primary alkanolamines and secondary alkanolamines having 2 to 4 carbon atoms in the hydroxyalkyl radical. Fungicide or bacteriostatic agent. The fungicide or bacteriostatic agent according to claim 4 or 5, further comprising a water-soluble fungicide which is stable to alkali. 8. The fungicide or bacteriostatic agent according to claim 7, wherein the fungicide is pyrithione or a derivative thereof and / or an N-alkyl-diagenium dioxide salt. The fungicide or bacteriostatic agent according to claim 4 or 5, wherein the aqueous system is a cooling lubricant. 8. The aqueous system according to claim 7, wherein the aqueous system is 0.05 to 0.40% by weight of the 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivative of general formula (I) and the fungicide A bactericide or bacteriostatic agent containing 0.0001 to 0.2% by weight.